Process for the production of substituted vinylbenzenes

ABSTRACT

A process for the production of substituted vinylbenzenes of the general formula: ##STR1## wherein R is a lower alkyl group having 1 to 4 C atoms, R 1  is hydrogen or an acetyl group and R 2  is hydrogen, a lower alkyl group having 1 to 4 C atoms or a benzyl group. A trialkylhydroquinone is cyclized with an aldehyde to an acetal and the latter is pyrolized to the endproduct. The substituted vinylbenzenes are valuable intermediate products in the synthesis of antioxidants.

BACKGROUND OF THE INVENTION

1. Field Of The Invention

The invention relates to a process for the production of substitutedvinylbenzenes of general formula: ##STR2## wherein R is a lower alkylgroup having 1 to 4 C atoms, R₁ is a hydrogen or an acetyl group and R₂is a hydrogen, a lower alkyl group having 1 to 4 C atoms or a benzylgroup.

2. Background Art

Substituted vinylbenzenes are valuable intermediate products for theproduction of antioxidants, such as, of Trolox C® (U.S. Pat. No5,080,886).

It is known from Chem. Berichte, Vol. 92, (1959), page 2958, that1-vinyl-2,4,5-trimethyl-3,6-dihydroxybenzene can be produced over fourstages starting from trimethylhydroquinone or trimethylphenol. In suchprocess, especially the last stage, the decarboxylation of3,6-dihydroxy-2,4,5-trimethyl cinnamic acid proves to be extremelydifficult. Thus, the desired vinylbenzene was able to be obtained in ayield of only 4 percent relative to the cinnamic acid derivative used.

BROAD DESCRIPTION OF THE INVENTION

The main object is to provide a process that does not have the abovespecified drawbacks and with which it is possible to produce thesubstituted vinylbenzenes on an industrial scale. Other objectives andadvantages of the invention are set out herein or are obvious herefromto one skilled in the art.

The objectives and advantages of the invention are achieved by theprocess and compounds of the invention.

The invention involves a process for the production of the substitutedvinylbenzenes of the general formula: ##STR3## wherein R is a loweralkyl group having 1 to 4 C atoms, R₁ is hydrogen or an acetyl group andR₂ is hydrogen, a lower alkyl group having 1 to 4 C atoms or a benzylgroup. A trialkylhydroquinone of the general formula: ##STR4## wherein Rhas the mentioned meaning, is reacted with an aldehyde of the generalformula: ##STR5## wherein R₂ has the mentioned meaning, in the presenceof an acid with exclusion of water to an acetal of the general formula:##STR6## wherein R and R₂ have the mentioned meanings. This acetal isoptionally reacted with acetyl chloride to the acetylated acetal of thegeneral formula: ##STR7## wherein R and R₂ have the mentioned meanings.Finally, the acetal of the general formula IV or V is pyrolized to avinylbenzene of the general formula: ##STR8## wherein R, R₁ and R₂ havethe mentioned meanings.

Preferably the trimethyl derivative with R being CH₃ is used as thetrialkylhydroquinone of the general formula II and the acetylaldehydewith R₂ being hydrogen is used as the aldehyde of the general formulaIII. Preferably the reaction to the acetal of general formula IV isperformed at a temperature between -30° to 30° C. in the presence of aninert solvent. Preferably hydrochloric acid is used a the acid for thereaction to the acetal of the general formula IV. Preferably theacetylation to the acetal of the general formula V takes place withacetyl chloride in the presence of a tertiary amine at a temperaturebetween 0° and 100° C. Preferably the pyrolysis of the acetal of thegeneral formula IV or V takes place at a temperature of over 300° C.under reduced pressure. Preferably the pyrolysis of the acetal of thegeneral formula IV or V takes place at a temperature between 400° and500° C. and a reduced pressure between 0.5 and 100 mbar.

The invention also involves acetals of the general formula: ##STR9##wherein R is a lower alkyl group having 1 to 4 C atoms, R₁ is hydrogenor an acetyl group and R₂ is hydrogen, a lower alkyl group having 1 to 4C atoms or a benzyl group. Preferably the acetal of the general formulaVIII is 2,4,5,7,8-pentamethyl-4H[1,3]dioxin-ol of the formula: ##STR10##

The invention further involves substituted vinylbenzenes of the generalformula: ##STR11## wherein R is a lower alkyl group having 1 to 4 Catoms, R₁ is a hydrogen or an acetyl group and R₂ is hydrogen, a loweralkyl group having 1 to 4 C atoms or a benzyl group. Preferably thesubstituted vinylbenzene of the general formula I is aceticacid-4-hydroxy-2,5-6-trimethyl-3-vinylphenyl ester of the formula:

DETAILED DESCRIPTION OF THE INVENTION

According to the invention process, in the first stage, atrialkylhydroquinone of the general formula: ##STR13## wherein R has theabove-mentioned meaning, is reacted with an aldehyde of the generalformula: ##STR14## wherein R₂ has the above-mentioned meaning, in thepresence of an acid and with exclusion of water to the acetal of thegeneral formula: ##STR15## wherein R and R₂ have the above-mentionedmeanings. Preferably trimethylhydroquinone is reacted with acetaldehydeto the corresponding acetal of the general formula IV with R being CH₃and R₂ being hydrogen. Suitably the reaction takes place at atemperature between -30° to 30° C., preferably at a temperature under20° C., in the presence of an inert solvent. Suitably the aldehyde isused in excess. Suitable anhydrous acids are, e.g., hydrochloric acid,hydrobromic acid, sulfuric acid and methanesulfonic acid. Preferablyhydrochloric acid is used.

The acetals of the general formula IV resulting in good yields can beisolated from the reaction mixture in ways known in the art.

The acetals of the general formula IV so far have not been described inthe prior art and therefore are also part of the invention. Thepreferred acetal of the general formula IV is the compound with R beingCH₃ and R₂ being hydrogen.

If desired the acetals of the general formula IV can be acetylated toacetylated acetals of the general formula: ##STR16## wherein R and R₂have the above-mentioned meanings. These acetals so far have also notbeen described in the prior art and, therefore, are also part of theinvention. The preferred acetylated acetal of the general formula V isthe compound with R being CH₃ and R₂ being hydrogen.

The acetylation takes place suitably with acetyl chloride in thepresence of a tertiary amine, such as, triethyl amine, in a suitableinert solvent. Usually the reaction takes place practicallyquantitatively at a temperature between 0° and 100° C.

The acetylated acetal can be isolated from the reaction mixture in theusual way and fed to the further reaction (pyrolysis).

In the next stage, the acetals of the general formula IV or V arepyrolyized to the substituted vinylbenzenes of the general formula:##STR17## wherein R, R₁ and R₂ have the above-mentioned meanings. Thepyrolysis takes place suitably at a temperature of over 300° C., (up tothe highest effective pyrolysis temperature), preferably between 400°and 500° C., at a reduced pressure of between 0.5 and 100 mbar.

Corresponding to the preferred acetals of the general formula IV or Vwith R being CH₃ and R₂ being hydrogen, the methylated derivatives withR being CH₃, R₁ being hydrogen or acetyl and R₂ being hydrogen resultedas the preferred vinylbenzenes of the general formula I.

The acetylated vinylbenzenes of the general formula I with R₁ beingacetyl so far have not been described in the prior art and, therefore,are also part of the invention.

The corresponding vinylbenzenes can be obtained in this way in a goodyield of about 70 percent relative to the trialkylhydroquinone used.

EXAMPLE 1 (a) Process for the production of2,4,5,7,8pentamethyl-4H-benzene[1,3]dioxin-6-ol

Trimethylhydroquinone (60.8 g, 0.4 mol) was suspended in CH₂ Cl₂ (1 1).A solution of acetaldehyde (135 ml, 105.6 g, 2.4 mol) in CH₂ Cl₂ (280ml) was added to this suspension so that the temperature did not exceed20° C. Then the suspension was saturated with gaseous HCl until thereaction was complete (tracked with TLC, toluene/acetone, 4:1). Thesuspension gradually dissolved during the HCl-addition. The yellowsolution was concentrated by evaporation under vacuum. 83 g (93.7percent) of yellow solid with a melting point of 101° to 1-3° C. wasobtained. Other data for the product was:

    ______________________________________                                        .sup.1 H-NMR: (C.sub.6 D.sub.6, 300MHz) δ in ppm                                              5.21(q, 1H, J=7Hz);                                                           4.87(q, 1H, J=6Hz);                                                           3.78(s, 1H);                                                                  2.21(s, 3H);                                                                  1.94(s, 3H);                                                                  1.69(s, 3H);                                                                  1.52(d, 3H, J=5Hz);                                                           1.28(d, 3H, J=6Hz) ;                                    Isomer:               5.01(q, 1H, J=6Hz);                                                           4.83(q, 1H, J=5Hz);                                                           3.82(s, 3H);                                                                  1.93(s, 3H);                                                                  1.78(s, 3H);                                                                  1.50(d, 3H, J=5Hz);                                                           1.42(d, 3H, J-6Hz).                                     ______________________________________                                    

(b) Process for the production of1,4-dihydroxy-2,3,5-trimethyl-6-vinylbenzene

(2 g, 9.0 mmol) of 2,4,5,7,8-pentamethyl-4H-benzene[1,3]dioxin-6-ol waspyrolized under vacuum (20 mbar) in a quartz tube at 460° C. A lightbrown solid (1 g, 62 percent) with a melting point of 143° to 145° C.was obtained. Other data for the production was:

    ______________________________________                                        .sup.1 H-NMR: (CDCl.sub.3, 300MHz) δ in ppm                                                  6.67(dd, 1H, J=12.5Hz,                                                        19Hz);                                                                        5.68(d, 1H, J=12.5Hz);                                                        5.50(d, 1H, J=19Hz);                                                          5.33(s, 1H);                                                                  4.25(s, 1H);                                                                  2.20(s, 6H);                                                                  2.13(s, 3H);                                             ______________________________________                                    

EXAMPLE2 (a) Process for the production of acetic acid2,4,5,7,8-penta-methyl-4H-benzene[1,3]dioxin-6-yl ester

2,4,5,6,8-Pentamethyl-4H-benzene[1,3]dioxin-6-ol (117.4 g, 0.528 mol)and triethylamine (63.14 g, 0.624 mol) were dissolved in CH₂ Cl₁ (800ml) at 0° C. Acetyl chloride (49.0 g, 0.624 mol) was instilled in thissolution during 1 hour. This mixture was stirred for 30 minutes and thenmixed with water (400 ml). the organic phase was dried with MgSO₄ andconcentrated by evaporation under vacuum. A light yellow solid (130.1 g,93 percent) with a melting point of 91.8° to 92.2° C. was obtained.Other data for the product was:

    ______________________________________                                        .sup.1 H-NMR: (CDCl.sub.3, 300MHz) δ in ppm                                                  5.34(q, 1H, J=7.5Hz);                                                         4.98(q, 1H, J=7.5Hz);                                                         2.35(s, 3H);                                                                  2.13(s, 3H);                                                                  2.04(s, 3H);                                                                  1.95(s, 3H);                                                                  1.54(d, 3H, J=7.5Hz);                                                         1.52(d, 3H, J=7.5Hz);                                    Isomer:              5.20(q, 1H, J=7.5Hz);                                                         4.96(q, 1H, J=7.5Hz);                                                         2.35(s, 3H);                                                                  2.13(s, 3H);                                                                  2.04(s, 3H);                                                                  1.99(d, 3H);                                                                  1.54(d, 3H, J=7.5Hz);                                                         1.47(d, 3H, J=7.5Hz).                                    ______________________________________                                    

(b) Process for the production of aceticacid-4-hydroxy-2,5,6-trimethyl-3-vinylphenyl ester

Acetic acid-2,4,5,7,8-pentamethyl-4H-benzene[1,3]dioxin-6-yl ester (20g, 75.6 mmol) was pyrolized in a quartz tube at 450° C. under vacuum (10mbar). After recrystallization from hexane (65 ml), a white solid (14.80g, 77 percent) with a melting point of 73.5° to 74.8° C. was obtained.Other data for the product was:

    ______________________________________                                        .sup.1 H-NMR: (CDCl.sub.3, 400MHz) δ in ppm                                                   6.63(dd, 1H, J=11.5&                                                          18.2Hz);                                                                      5.69(dd, 1H, J=1.8&                                                           11.5Hz);                                                                      5.58(s, 1H);                                                                  5.51(dd, 1H, J=1.8 &                                                          18.2Hz);                                                                      2.32(s, 3H);                                                                  2.17(s, 3H);                                                                  2.05(s, 3H);                                                                  2.01(s, 3H).                                            ______________________________________                                    

What is claimed is:
 1. A process for the production of a substitutedvinylbenzene of general formula: ##STR18## wherein, R is a lower alkylgroup having 1 to 4 C atoms, R₁ is hydrogen or an acetyl group and R₂ ishydrogen, a lower alkyl group having 1 to 4 C atoms or a benzyl group,characterized in that a trialkylhydroquinone of general formula:##STR19## wherein R has the above-stated meaning, is reacted with analdehyde of general formula: ##STR20## wherein R₂ has the above-statedmeaning, in the presence of an acid with exclusion of water to an acetalof general formula: ##STR21## wherein R and R₂ have the above-mentionedmeanings, this acetal is optionally reacted with acetyl chloride to theacetylated acetal of general formula: ##STR22## wherein R and R₂ havethe above-mentioned meanings, and, finally, the acetal of the generalformula IV or V are pyrolized to the vinylbenzene of the generalformula: ##STR23## wherein R, R₁ and R₂ have the above-mentionedmeanings.
 2. The process according to claim 1 wherein the trimethylderivative with R being CH₃ is used as the trialkylhydroquinone of thegeneral formula II and the acetylaldehyde with R₂ being hydrogen is usedas aldehyde of the general formula III.
 3. The process according toclaim 2 wherein the reaction to the acetal of the general formula IV isperformed at a temperature between -30° to 30° C. in the presence of aninert solvent.
 4. The process according to claim 3 wherein hydrochloricacid is used as the acid for the reaction to the acetal of the generalformula IV.
 5. The process according to claim 4 wherein the acetylationto the acetal of the general formula V takes place with acetyl chloridein the presence of a tertiary amine at a temperature between 0° C. and100° C.
 6. The process according to claim 1 wherein the pyrolysis of theacetal of the general formula IV or V takes place at a temperature ofover 300° C under reduced pressure.
 7. The process according to claim 6wherein the pyrolysis of the acetal of the general formula IV or V takesplace at a temperature between 400° and 500° C. and a reduced pressurebetween 0.5 and 100 mbar.
 8. The process according to claim 1 whereinthe reaction to the acetal of the general formula IV is performed at atemperature between -30° to 30° C. in the presence of an inert solvent.9. The process according to claim 1 wherein hydrochloric acid is used asthe acid for the reaction to the acetal of the general formula IV. 10.The process according to claim 1 wherein the acetylation to the acetalof the general formula V takes place with acetyl chloride in thepresence of a tertiary amine at a temperature between 0° C. and 100° C.11. The process according to claim 6 wherein the pyrolysis of the acetalof the general formula IV or V takes place at a temperature between 400°and 500° C. and a reduced pressure between 0.5 and 100 mbar.